Process for producing n-alkylpyrazoles

ABSTRACT

Disclosed herein is a process for producing N-alkylpyrazoles represented by the formula (1), which comprises reacting an alkali metal or an alkali metal-containing base with N- unsubstituted pyrazoles represented by the formula (2), to form an alkali metal salt thereof and, subsequently, reacting the obtained alkali metal salt with an alkylating agent. ##STR1##

This application is a continuation of application Ser. No. 07/913,194filed on Jul. 14, 1992 now abandoned, which was a Continuation-in-partof Ser. No. 07/678,241 filed Apr. 1, 1991, now U.S. Pat. No. 5,153,329.

BACKGROUND OF THE INVENTION

The present invention relates to a process for producing N-alkylpyrazoles which are useful as an intermediate for medicines andagricultural chemicals, in particular, as an intermediate forherbicides.

As for the N-alkylation method for pyrazoles, methods to be describedhereinafter have been known.

(1) A method of reacting 4-methylpyrazole and dimethyl sulfate in anaqueous 2N solution of sodium hydroxide is disclosed in Justus LiebigsAnnal.en der Chemie, 625, 55 (1959). However, the yield of1,4-dimethylpyrazole in this method is as low as 56%.

(2) A method of reacting 3(5)-methylpyrazole and methyl iodide in thepresence of sodium methoxide in a methanol solution to obtain1.3-dimethylpyrazole and 1,5-dimethylpyrazole is disclosed in ChemischBerichte, 59, 1282 (1926). However, no satisfactory results areobtainable by this method (refer to Comparative Examples 1 and 2 to bedescribed later).

It has strongly be demanded for providing a process for producingN-alkylpyrazoles useful as an intermediate for medicines andagricultural chemicals at a high yield.

As a result of the present inventors earnest study for satisfying theforegoing demand, it has been found that N-alkylpyrazoles represented bythe formula (1) can be obtained at a high yield by reacting an alkalimetal or an alkali metal-containing base with N- unsubstituted pyrazolesrepresented by the formula (2) to form an alkali metal salt thereof and,subsequently, reacting the obtained alkali metal salt of pyrazoles withalkylating agents. ##STR2## (wherein R¹ represents a hydrogen atom or aC₁ -C₄ alkyl group, R² represents a C₁ -C₄ alkyl group and n representsan integer of 1 to 3)

The present invention has been attained on the basis of theabove-mentioned finding.

SUMMARY OF THE INVENTION

In an aspect of the present invention, there is provided a process forproducing N-alkylpyrazoles represented by the formula (1), whichcomprises reacting an alkali metal or an alkali metal-containing basewith N- unsubstituted pyrazoles represented by the formula (2) to forman alkali metal salt thereof and, subsequently, reacting the obtainedalkali metal salt of pyrazoles with on alkylating agent. ##STR3##(wherein R¹ represents a hydrogen atom or a C₁ -C₄ alkyl group and R²represents a C₁ -C₄ alkyl group and n represents an integer of 1 to 3)

DETAILED DESCRIPTION OF THE INVENTION

As the alkali metal or the alkali metal-containing base, there can beused an inorganic base such as sodium hydride, potassium hydride,lithium hydride, sodium metal potassium, metal lithium metal, lithiumaluminum hydride, sodium borohydride, lithium borohydride, butyllithium, lithium diisopropylamide, sodium hydroxide, potassiumhydroxide, lithium hydroxide, sodium carbonate and potassium carbonate,and an organic base such as sodium methoxide, sodium ethoxide, potassiummethoxide, potassium ethoxide, potassium t-butoxide, trimethylamine,triethylamine and pyridine.

A preferred amount of the alkali metal or alkali metal-containing baseused is within a range usually from 0.7 to 5.0 mol, preferably 1.0 to2.0 mol based on one mol of N-unsubstituted pyrazoles. The reactiontemperature is from -10° to 200° C. and the reaction time is from 0.5 to30 hours.

As the alkylating agent, there can be mentioned alkyl halide such asmethyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethylbromide, ethyl iodide, propyl chloride, propyl bromide, propyl iodide,isopropyl chloride, isopropyl bromide, isopropyl iodide and butylbromide, and dimethyl sulfate and diethyl sulfate.

A preferred amount of the alkylating agent used is within a rangeusually from 0.4 to 10.0 mol, preferably 0.5 to 5.0 mol based on one molof N- unsubstituted pyrazoles. The reaction temperature is usuallywithin range from -10° to 200° C. and the reaction time is from 0.5 to30 hours.

The reaction of the present invention can be conducted without solventbut a solvent may be used. As the solvent, there can be mentionedaliphatic hydrocarbons such as hexane and heptane; halogenatedhydrocarbons such as methylene chloride and 1,1,1-trichloroethane;aromatic hydrocarbons such as benzene, toluene and xylene;halogen-substituted aromatic hydrocarbons such as chlorobenzene,dichlorobenzene and 3,4-dichlorotoluene; alkoxy-substituted aromatichydrocarbons such as anisole and 1,2-dimethoxybenzene; ethers such asdiethyl ether, dipropyl ether, methyl tertiary butyl ether, ethyleneglycol dibutyl ether, diethylene glycol dibutyl ether, tetrahydrofuranand dioxane; and aprotic polar solvents such as N,N'-dimethylformamideand acetonitrile ketone, diethyl ketone, diisopropyl ketone anddiisobutyl ketone, the preferred being methylpropyl ketone,methylisopropyl ketone, methylisobutyl ketone, methyl-t-butyl ketone,diethyl ketone, diisopropyl ketone and diisobutyl ketone. In addition,for forming the alkali metal salt of pyrazoles, alchols such asmethanol, ethanol, butanol and amylalcohol can also be used. Two or moreof the above-mentioned solvents can also be used as mixture ordispersion.

The reaction of the present invention can be applied either in anatmospheric pressure or under pressure.

In particular, an alkali metal salt of N- unsubstituted pyrazoles can beproduced industrially at a good yield by the following methods.

The first method is a process for producing an alkali metal salt of N-unsubstituted pyrazoles by reacting N-unsubstituted pyrazoles withsodium metal or potassium metal, etc. The reaction may be proceededwithout solvent but the inert solvent as described above may also beused. Further, sodium metal, potassium metal or the like may be used assuch in the state of solid but it is preferred to react them in a moltenstate.

Alternatively, the second method is a process for producing an alkalimetal salt of pyrazoles at a good efficiency by reacting N-unsubstituted pyrazoles with sodium methoxide, sodium ethoxide,potassium methoxide, potassium ethoxide, potassium t-butoxide, sodiumhydroxide, potassium hydroxide, lithium hydroxide, etc., whiledistilling off alcohol or water.

Generally, a strongly acidic N- unsubstituted pyrazoles having a strongelectron attracting group such as a carboxylic acid ester group or anitro group as a substituent can easily form a salt with a base, butweakly acidic N- unsubstituted pyrazoles as N- unsubstituted alkylpyrazole according to the present invention hardly form a salt. Forinstance, reaction of an alkoxide such as sodium methoxide with N-unsubstituted pyrazoles in an alcohol solvent followed by a treatmentwith the alkylating agent described above can provide no satisfactoryresults (refer to Comparative Examples 1 and 2) . This is considered tobe attributable to that a sodium salt of pyrazoles can not be formedefficiently due to the following equilibrium reaction. ##STR4## (whereinR¹ represents a hydrogen atom or a C₁ -C₄ alkyl group and Q represents ahydrogen atom or methyl group)

In view of the above, an alkali metal salt of methyl pyrazoles can beformed at a good efficiency by distilling off alcohol or water out ofthe reaction system, thereby shifting the above-mentioned equilibriumreaction rightward. The reaction can be conducted also in thecoexistence of an inert solvent.

Referring to embodiments for practicing the present invention, the firstmethod is a process for obtaining N-alkylpyrazoles represented by theformula (1) by reacting N-unsubstituted pyrazoles with an alkali metalat 60° to 190° C. for 0.5 to 5.0 hours, thereby obtaining an alkalimetal salt of pyrazoles and, subsequently, reacting the obtaining alkalimetal salt of pyrazoles with an alkylating agent at 20° to 150° C. for1.0 to 20 hours.

The second method is a process for obtaining N-alkylpyrazolesrepresented by the formula (1) by reacting N-unsubstituted pyrazoleswith alkoxides or alkali hydroxides while distilling off alcohol orwater to form an alkali metal salt of pyrazoles and, subsequently,reacting the obtained alkali metal salt of pyrazoles with an alkylatingagent at 20° to 150° C. for 1.0 to 20 hours.

After finishing the reaction, inorganic materials in the reactionproduct are removed by filtration or adding water to the reactionmixture and extracting the reaction product with an organic solvent and,subsequently, N-alkylpyrazoles represented by the formula (1) can beobtained by means of distillation or the like.

In accordance with the present invention, N-alkylation for N-unsubstituted pyrazoles can be conducted also within an industrial scaleand N-alkylpyrazoles represented by the formula (1) can be obtained at ahigh yield.

In particular, the present invention is effective as a process forproducing 1,4-dimethylpyrazole. 1,4-dimethylpyrazole useful as anintermediate for herbicides [refer to Japanese Patent ApplicationLaid-Open (KOKAI) 60-208977 (Corresponding to U.S. Pat. Nos. 4,668,277and 4,689,417)] used in corn farms (Japanese Patent ApplicationLaid-Open (KOKAI) 2-191259).

As shown in Comparative Examples 1 and 2 described later, the conversionratio is low and the yield of N-alkylpyrazoles is lower than 50% in theconventional method, whereas in the present invention the conversionratio is high, for example, not lower than 80% and the yield ofN-alkylpyrazoles is not lower than 80%, and depending on the reactionconditions, it can be obtained at a high yield of not lower than 95%.

EXAMPLE

The present invention will be explained referring to examples but thepresent invention is not restricted to them.

EXAMPLE 1

In 5 g of dry toluene, 0.25 g (0. 0109 mol) of metal sodium was put to amolten state at a temperature of 100° to 105° C., to which 1.0 g (87.8%purity, 0.0107 mol) of 4-methylpyrazole was added under stirring for 10min. After the dropping was over, it was stirred for further 45 min at100° to 105° C. and then the temperature was returned to a roomtemperature. After adding 6 ml of tetrahydrofuran, 1.60 g (0.0113 mol)of methyl iodide was dropped for 5 min and, after stirring for 3 hours,inorganic matters were separated by filtration. When the liquid filtratewas analyzed on liquid chromatography, 0. 89 g of 1,4-dimethylpyrazolewas contained therein. The conversion ratio was 88% and the yield was87% based on 4-methylpyrazole.

EXAMPLE 2

0.25 g (0.0109 mol) of metal sodium was put to a molten state in areflux of 5 g of dry dioxane, to which 1.0 g (87.8% purity, 0.0107 mol)of 4-methylpyrazole was dropped for 10 min under stirring. After thedropping was over, they were further stirred for 5 hours in a refluxingstate and then the temperature was returned to a room temperature. Afterdropping 1.60 g (0.0113 mol) of methyl iodide for 5 min and stirring for2 hours, inorganic matters were separated by filtration. When the liquidfiltrate was analyzed on liquid chromatography, 0.91 g of1,4-dimethylpyrazole was contained therein. The conversion ratio was 91%and the yield was 88% based on 4-methylpyrazole.

EXAMPLE 3

0.27 g (0.0117 mol) of metal sodium was added to 1.7 g of dry methanolat a room temperature and solved under stirring to prepare sodiummethoxide. After adding 5 g of heptane, 1.0 g (87.8% purity, 0.0107 mol)of 4-methylpyrazole was dropped for 5 min under stirring. After stirringat a room temperature for 30 min, the temperature was elevated to 80° C.and methanol was distilled off for one hour and, further, methanol wasdistilled off at 90° C. for one hour. After returning the temperature toa room temperature and adding 5 g of tetrahydrofuran, 1.67 g (0.0118mol) of methyl iodide was dropped for 5 min. After stirring for 4 hours,inorganic matters were separated by filtration. When the liquid filtratewas analyzed on liquid chromatography, 0.96 g of 1,4-dimethylpyrazolewas contained therein. The yield was 94% based on 4-methylpyrazole.

EXAMPLE 4

0.27 (0.0117 mol) of metal sodium was put to a molten state in reflux of5 g of dry dioxane, to which 1.0 g (87.8% purity, 0.0107 mol) of4-methylpyrazole was dropped for 2 min under stirring. After thedropping was over, they were further stirred for 4 hours and 20 min in arefluxing state, and then the temperature was returned to 40° C. 6.48 g(0.1284 mol) of methyl chloride was blown at 40° C. for hours and at 50°C. for 2 hours, and thereafter, inorganic matters were separated byfiltration. When the liquid filtrate was analyzed on liquidchromatography, 1.02 of 1,4-dimethylpyrazole was contained therein. Theyield was 99% based on 4-methylpyrazole.

EXAMPLE 5

0.51 g (0.0119 mol) of 93% sodium hydroxide was added to 2.1 g of drymethanol and dissolved at 50° C. After adding 5 g of heptane, 1.0 g(87.8% purity, 0.0107 mol) of 4-methylpyrazole was dropped understirring for 5 min. After stirring for 30 min, the temperature waselevated and methanol was distilled off at 75° to 90° C. for 2.0 hours.Subsequently, the temperature was returned to a room temperature. 5 g oftetrahydrofuran was added and 1.67 g (0.0118 mol) of methyl iodide wasdropped for 5 min. After stirring for 5 hours, inorganic matter wereseparated by filtration. When the liquid filtrate was analyzed on liquidchromatography. 1.0 g of 1,4-dimethylpyrazole was contained therein, theconversion ratio was 98% and the yield was 97% based on4-methylpyrazole.

EXAMPLE 6

0.51 g (0.0119 mol) of 93% sodium hydroxide was added to 2.1 g of drymethanol and dissolved at 50° C. After adding 5 g of heptane, 1.0 g(87.8% purity, 0. 0107 mol) of 4-methylpyrazole was dropped understirring for 5 min. After stirring for 30 min, the temperature waselevated and methanol was distilled out at 75° to 95° C. for 2.5 hours.Subsequently, the temperature was returned to a room temperature, 5 g oftetrahydrofuran was added and 1.87 g (0.0168 mol) of 98% ethyl bromidewas dropped for 5 min. After stirring for 2 hours, the temperature waselevated to 40° C. and the stirring was continued for 14.5 hours. Afterseparating inorganic matters by filtration, when the liquid filtrate wasanalyzed on liquid chromatography, 1.04 g of 1-ethyl-4-methylpyrazolewas contained therein, the conversion ratio was 94% and the yield was89% based on 4-methylpyrazole.

EXAMPLE 7

0.57 g (0.0133 mol) of 93% sodium hydroxide was added to 2.3 g of drymethanol and dissolved at 50° C. After adding 5 g of heptane, 1.0 g (99%purity, 0.0121 mol) of 4-methylpyrazole was dropped under stirring for10 min. After stirring for 30 min, the temperature was elevated andmethanol was distilled off at 70° to 90° C. for one hour. Then, thetemperature was lowered to 40° C., 5 g of tetrahydrofuran was added and2.26 g (0.0133 mol) of isopropyl iodide was dropped for 7 min. andstirred for 4 hours. The temperature was further elevated and stirringwas applied for 33 hours while refluxing under heating. After separatinginorganic matters by filtration, when the liquid filtrate was analyzedon liquid chromatography, 1.13 g of 1-isopropyl-4-methylpyrazole wascontained therein. The conversion ratio was 86% and the yield was 83 %based on 4-methylpyrazole. Boiling point was 61°-65° C./18 mmHg.

EXAMPLE 8

After adding a solution of 1.08 g (0.0251 mol) of 93% sodium hydroxidedissolved in 6 g of methanol to a liquid mixture containing 2.0 g (93.5%purity, 0.0228 mol) of 4-methylpyrazole and 10 g of chlorobenzene,temperature was elevated and methanol was distilled off at 100° C. of anouter bath. Then, the temperature was lowered and methyl chloride wasblown at 50°-55° C. at a rate of 10 ml per one min for 9 hours. Afterseparating inorganic matters by filtration, when the filtrate wasanalyzed on liquid chromatography, 2.15 g of 1,4-dimethylpyrazole wascontained therein, the yield was 98% based on 4-methylpyrazole.

EXAMPLE 9

After adding a solution of 1.08 g (0.0251 mol) of 93% sodium hydroxidedissolved in 6 g of methanol to a liquid mixture containing 2.0 g (98.5%purity, 0.0228 mol) of 4-methylpyrazole and 45 g of methyl tertiarybutyl ether, the temperature was elevated and methanol was distilled offat 51°-53° C. by azeotropic boiling with methyl tertiary butyl ether.Then, methyl chloride was blown at 50°-55° C. at a rate of 10 ml per onemin for 18 hours. After separating inorganic matters by filtration, whenthe filtrate was analyzed on liquid chromatography, 2.02 g of1,4-dimethylpyrazole was contained therein. The conversion ratio was 93%and the yield was 92% based on 4-methylpyrazole.

EXAMPLE 10

After adding a solution of 1.08 g (0.0251 mol) of 93% sodium hydroxidedissolved in 5 g of methanol to a liquid mixture containing 2.0 g (93.5%purity, 0.0228 mol) of 4-methylpyrazole and 10 g of1,2-dimethoxybenzene, temperature was elevated and methanol wasdistilled off at 100° C. of an outer bath. Then, the temperature waslowered and methyl chloride was blown at 50°-55° C. at a rate of 10 perone min for 3.5 hours. After separating inorganic matters by filtration,when the filtrate was analyzed on liquid chromatography, 2.17 g of1,4-dimethylpyrazole was contained therein. The yield was 99% based on4-methylpyrazole.

EXAMPLE 11

1.10 g (0.0478 mol) of metal sodium was added to 10 g of dry methanol toprepare sodium methoxide. After adding 20 g of heptane, 4.0 g (0.0488mol) of 3-methylpyrazole was dropped under stirring for 5 min. Afterstirring for 30 min, the temperature was elevated and methanol wasdistilled off at 75°-90° C. for 2.0 hours. Then, the temperature wasreturned to a room temperature, 20 g of tetrahydrofuran was added and9.26 (0.0652 mol) of methyl iodide was dropped for 5 min. After stirringfor 2 hours, inorganic matters were separated by filtration. When theliquid filtrate was analyzed on gas chromatography, 4.3 g of a mixturecontaining 1,3-dimethylpyrazole and 1,5-dimethylpyrazole at 1:1.7 ratiowas contained. The conversion ratio was 93% and the yield was 92% basedon 3-methylpyrazole.

EXAMPLE 12

To a mixture of 0.8 g of 4-methylpyrazole (purity 93.8%, 0.00915 moles)and 3.0 g of methylisobutyl ketone was added 0.5 g (0.0116 moles) of 93%sodium hydroxide. After stirring the mixture at a temperature of 50°-55°C. for 30 min., about 2 liters of methyl chloride was blown therethroughwith ice-cooling and the mixture was then heated to a temperature of50°-55° C. followed by 4.5 hr-stirring. After cooling 5 g of water wasadded to the reaction mixture to dissolve inorganic matters, and 5 g ofmethylisobutyl ketone was subsequently added so as to extract organicmatters. The aqueous layer was extracted twice with 5 g portions ofmethylisobutyl ketone. When the combined organic extracts were analyzedon liquid chromatography, 0.86 g of 1,4-dimethylpyrazole was containedtherein. The yield was 98% based on 4-methylpyrazole.

EXAMPLE 13

To a mixture of 158.5 g (3.1706 moles) of hydrazine monohydrate, 793 gof ethanol and 256 g of water was added 331 g of 35% aqueoushydrochloric acid solution to form hydrazine hydrochloride. 413.49 g(2.6422 moles) of 90.1% 2,3-dichloro-2-methylpropanal was then addeddropwise over 2 hr with stirring and maintaining the reactiontemperature at 74°-84° C. At the same time, 40% aqueous sodium hydroxidesolution was also added dropwise in order to adjust the pH to 3-5. Afteraddition, the reaction mixture was further stirred at a temperature of74°-84° C. and pH 3-5 for 1.5 hr, from which ethanol was then distilledaway at a boiling point of 64° C./400 mmHg-68° C./380 mmHg. The residuewas cooled to room temperature to which 49 g of 40% aqueous sodiumhydroxide solution was then added in order to alkalinize. To the mixturewas added 520 g of water and 397 g of methylisobutyl ketone, and theorganic layer was then separated while the aqueous layer was extractedthree times with 132 g portions of methylisobutyl ketone. When theaqueous extracts were analyzed on liquid chromatography,4-methylpyrazole was not detected. When the combined organic liquid wassimilarly analyzed on liquid chromatography, 171.7 g of 4-methylpyrazolewas contained therein. The yield was 79% based on2,3-dichloro-2-methylpropanal.

Then, the combined organic liquid was subjected to azeotropicdistillation to remove water at 84°-91° C. and 113 6 g (2.6422 moles) of93% sodium hydroxide was added followed by 30 min-stirring at 55° C.After reducing the pressure up to 55° C./90 mmHg, 134 g (2.6422 moles)of methyl chloride was blown through the mixture over 3.5 hr and thenstirred at 55° C. for 1 hr. The temperature was subsequently returned toroom temperature and 459 g of water was added to dissolve inorganicmatters. After separation of the organic layer, the aqueous layer wasextracted twice with 115 g portions of methylisobutyl ketone. When thecombined organic liquid was analyzed on liquid chromatography, 197.0 gof 1,4-dimethylpyrazole was contained therein. The yield was 98% basedon 4-methylpyrazole.

COMPARATIVE EXAMPLE 1

0.50 g (0.0218 mol) of metal sodium was added at a room temperature to20 g of dry methanol to prepare sodium methoxide. 2.0 g (84.9% purity,0.0207 mol) of 4-methylpyrazole was dropped for 5.0 min and stirring wasfurther applied at a room temperature for 30 min. 3.09 g (0.0218 mol) ofmethyl iodide was dropped for 6 min and after the completion of thedropping, the resultant mixture was stirred for 5.5 hours at a roomtemperature and for 3 hours at a methyl iodide refluxing temperature.Since the conversion ratio was low, 3.09 g (0.0218 mol) of methyl iodidewas further added and stirred for 7 hours at a refluxing temperature.When the reaction solution was analyzed on liquid chromatography, 0.73 gof 4-methylpyrazole and 1.00 g of 1,4-dimethylpyrazole were containedtherein. The conversion ratio was 63.5% and the yield was 50% based onthe 4-methylpyrazole.

COMPARATIVE EXAMPLE 2

0.55 g (0.0239 mol) of metal sodium was added at a room temperature to10 g of dry methanol to prepare sodium methoxide. 2.0 g (0.0244 mol) of3-methylpyrazole was dropped for 5.0 min and the stirring was furthercontinued at a room temperature for 30 min. 4.63 g (0.0326 mol) ofmethyl iodide was dropped for 20 min and, after completion of thedropping, the resultant mixture was stirred for 5.0 hours at a roomtemperature. After distilling off methanol, 20 g of water was added todissolve inorganic matters and the organic matters were extracted with20 g of diethyl ether. The aqueous layer was extracted for three timeswith 6 g of diethyl ether, and the obtained extract joined with theabove-mentioned organic layer. When the obtained organic layer wasanalyzed on gas chromatography and liquid chromatography, 1.30 g of3-methylpyrazole and 0.77 g of a mixture containing 1,3-dimethylpyrazoleand 1.5-dimethylpyrazole at 1:1.1 ratio were contained. The conversionratio was 35% and the yield was 33% based on 3-methylpyrazole.

What is claimed is:
 1. A process for producing N-alkylpyrazolesrepresented by Formula (I): ##STR5## wherein R¹ is a C₁ -C₄ alkyl groupand R² is a C₁ -C₄ alkyl group and n is an integer of 1 to 3, whichcomprises:reacting an alkali metal or an alkali metal-containing basewith a N-unsubstituted pyrazole represented by the Formula (2): ##STR6##wherein R¹ and n are defined above, thereby forming an alkali metal saltthereof; and, subsequently reacting the alkali metal pyrazole saltobtained with an alkylating agent in a solvent selected from the groupconsisting of an alkoxy-substituted aromatic hydrocarbon, and a ketone.2. The process according to claim 1, wherein said N-unsubstitutedpyrazole reactant has Formula (2a): ##STR7## wherein R¹ is as definedabove, and said N-alkylpyrazole product has Formula (1a): ##STR8##wherein R¹ and R² are as defined above.
 3. A process according to claim1, wherein the alkoxy-substituted aromatic hydrocarbon is anisole or1,2-dimethoxy-benzene; and the ketone is acetone, methylethyl ketone,methylpropyl ketone, methylisopropyl ketone, methylisobutyl ketone,methyl-t-butyl ketone, diethyl ketone, diisopropyl ketone or diisobutylketone.
 4. The process according to claim 1, wherein R² represents amethyl group.
 5. The process according to claim 1, wherein R¹ and R²each represents a methyl group.
 6. The process according to claim 1,wherein the alkali metal or the alkali metal containing base is at leastone selected from the group consisting of sodium hydride, potassiumhydride, lithium hydride, sodium metal, potassium metal, lithium metal,sodium hydroxide, potassium hydroxide, lithium hydroxide, sodiummethoxide, sodium ethoxide, potassium methoxide, potassium ethoxide,potassium t-butoxide, butyl lithium and lithium diisopropylamide.
 7. Theprocess according to claim 1, wherein sodium or potassium metal isreacted in the molten state with N-unsubstituted pyrazoles representedby the formula (2) to form an alkali metal pyrazole salt.
 8. The processaccording to claim 1, wherein at least one alkali metal-containing baseselected from the group consisting of sodium methoxide, sodium ethoxide,potassium methoxide, potassium ethoxide, potassium t-butoxide, sodiumhydroxide, potassium hydroxide and lithium hydroxide is reacted with anN-unsubstituted pyrazole represented by the formula (2) while distillingoff an alcohol or water to form an alkali metal pyrazole salt.
 9. Theprocess according to claim 1, wherein the alkylating agent is at leastone member selected from the group consisting of methyl chloride, methylbromide, methyl iodide, ethyl chloride, ethyl bromide, ethyl iodide,propyl chloride, propyl bromide, propyl iodide, isopropyl chloride,isopropyl bromide, isopropyl iodide, dimethyl sulfate and diethylsulfate.
 10. The process for according to claim 1, wherein the reactiontemperature is from -10° to 200° C. and ketones such as acetone,methylethyl ketone, methylpropyl ketone, methylisopropyl ketone,methylisobutyl ketone, methyl-t-butyl
 11. The process according to claim1, wherein the solvent selected is a ketone.
 12. The process accordingto claim 1, wherein the solvent selected is an alkoxy-substitutedaromatic hydrocarbon.
 13. The process according to claim 2, wherein thesolvent selected is a ketone.
 14. The process according to claim 2,wherein the solvent selected is an alkoxy-substituted aromatichydrocarbon.
 15. The process according to claim 1, wherein thealkylating agent is used in the amount of from 0.4 to 10.0 moles permole of N-unsubstituted pyrazole.
 16. The process according to claim 1,wherein the alkylating agent is used in the amount of 0.5 to 5.0 molesper mole of N-unsubstituted pyrazole.
 17. The process according to claim2, wherein the alkylating agent is used in the amount of 0.4 to 10.0moles per mole of N-unsubstituted pyrazole.
 18. The process according toclaim 2, wherein the alkylating agent is used in the amount of 0.5 to5.0 moles per mole of N-unsubstituted pyrazole.